RU2012108925A - HEAT EXCHANGE LAYER FROM CASCADE OF MAGNETO-CALORIC MATERIALS - Google Patents

HEAT EXCHANGE LAYER FROM CASCADE OF MAGNETO-CALORIC MATERIALS Download PDF

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RU2012108925A
RU2012108925A RU2012108925/07A RU2012108925A RU2012108925A RU 2012108925 A RU2012108925 A RU 2012108925A RU 2012108925/07 A RU2012108925/07 A RU 2012108925/07A RU 2012108925 A RU2012108925 A RU 2012108925A RU 2012108925 A RU2012108925 A RU 2012108925A
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heat transfer
transfer layer
layer according
magnetocaloric materials
thermal
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RU2012108925/07A
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Russian (ru)
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Колмэн-Патрик КЭРРОЛЛ
Олаф РОГГЕ
Бенни РЕЙСИНК
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Басф Се
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28C—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA COME INTO DIRECT CONTACT WITHOUT CHEMICAL INTERACTION
    • F28C3/00—Other direct-contact heat-exchange apparatus
    • F28C3/10—Other direct-contact heat-exchange apparatus one heat-exchange medium at least being a fluent solid, e.g. a particulate material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F7/00—Elements not covered by group F28F1/00, F28F3/00 or F28F5/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
    • B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
    • B23P15/26—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass heat exchangers or the like
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B21/00—Machines, plants or systems, using electric or magnetic effects
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F1/00—Tubular elements; Assemblies of tubular elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/012—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials adapted for magnetic entropy change by magnetocaloric effect, e.g. used as magnetic refrigerating material
    • H01F1/015—Metals or alloys
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2321/00—Details of machines, plants or systems, using electric or magnetic effects
    • F25B2321/002—Details of machines, plants or systems, using electric or magnetic effects by using magneto-caloric effects
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/4935—Heat exchanger or boiler making
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/4935—Heat exchanger or boiler making
    • Y10T29/49352—Repairing, converting, servicing or salvaging

Abstract

1. Теплообменный слой из каскада по меньшей мере трех различных магнетокалорических материалов с различными температурами Кюри, которые расположены друг за другом в порядке возрастания или убывания температуры Кюри и предпочтительно в каждом случае изолированы друг от друга расположенными между ними термическими и/или электрическими изоляторами, причем разность температур Кюри у соседствующих магнетокалорических материалов составляет от 0,5 до 4°С.2. Теплообменный слой по п.1, отличающийся тем, что разность температур Кюри соседствующих магнетокалорических материалов составляет от 1,5 до 2,5°С.3. Теплообменный слой по п.2, отличающийся тем, что разность температур Кюри соседствующих магнетокалорических материалов составляет от 1,8 до 2,2°С.4. Теплообменный слой по одному из пп.1-3, отличающийся тем, что в теплообменном слое присутствуют от 5 до 50 различных магнетокалорических материалов.5. Теплообменный слой по одному из пп.1-3, отличающийся тем, что термические и/или электрические изоляторы состоят из органического полимера, керамики, неорганических оксидов, углеродных волокон или сетей углеродных волокон, различных сортов стекла, полупроводников или сочетания этих компонентов.6. Теплообменный слой по одному из пп.1-3, отличающийся тем, что термические и/или электрические изоляторы образуют матрицу, в которую введены магнетокалорические материалы.7. Теплообменный слой по одному из пп.1-3, отличающийся тем, что расстояние между соседствующими магнетокалорическими материалами составляет от 0,05 до 3 мм.8. Теплообменный слой по одному из пп.1-3, отличающийся тем, что магнетокалорические материалы и термические и/или электр1. A heat transfer layer of a cascade of at least three different magnetocaloric materials with different Curie temperatures, which are arranged one after another in increasing or decreasing Curie temperatures and are preferably in each case insulated from each other by thermal and / or electrical insulators located between them, and the Curie temperature difference between adjacent magnetocaloric materials is from 0.5 to 4 ° C. 2. The heat exchange layer according to claim 1, characterized in that the Curie temperature difference of the adjacent magnetocaloric materials is from 1.5 to 2.5 ° C. The heat exchange layer according to claim 2, characterized in that the Curie temperature difference of adjacent magnetocaloric materials is from 1.8 to 2.2 ° C. A heat transfer layer according to one of claims 1 to 3, characterized in that from 5 to 50 different magnetocaloric materials are present in the heat transfer layer. A heat transfer layer according to one of claims 1 to 3, characterized in that the thermal and / or electrical insulators consist of an organic polymer, ceramic, inorganic oxides, carbon fibers or carbon fiber networks, various types of glass, semiconductors, or a combination of these components. 6. A heat exchange layer according to one of claims 1 to 3, characterized in that thermal and / or electrical insulators form a matrix into which magnetocaloric materials are introduced. A heat transfer layer according to one of claims 1 to 3, characterized in that the distance between adjacent magnetocaloric materials is from 0.05 to 3 mm. Heat transfer layer according to one of claims 1 to 3, characterized in that the magnetocaloric materials and thermal and / or electronic

Claims (15)

1. Теплообменный слой из каскада по меньшей мере трех различных магнетокалорических материалов с различными температурами Кюри, которые расположены друг за другом в порядке возрастания или убывания температуры Кюри и предпочтительно в каждом случае изолированы друг от друга расположенными между ними термическими и/или электрическими изоляторами, причем разность температур Кюри у соседствующих магнетокалорических материалов составляет от 0,5 до 4°С.1. A heat transfer layer of a cascade of at least three different magnetocaloric materials with different Curie temperatures, which are arranged one after another in increasing or decreasing Curie temperatures and are preferably in each case insulated from each other by thermal and / or electrical insulators located between them, and the Curie temperature difference between adjacent magnetocaloric materials is from 0.5 to 4 ° C. 2. Теплообменный слой по п.1, отличающийся тем, что разность температур Кюри соседствующих магнетокалорических материалов составляет от 1,5 до 2,5°С.2. The heat transfer layer according to claim 1, characterized in that the Curie temperature difference of adjacent magnetocaloric materials is from 1.5 to 2.5 ° C. 3. Теплообменный слой по п.2, отличающийся тем, что разность температур Кюри соседствующих магнетокалорических материалов составляет от 1,8 до 2,2°С.3. The heat transfer layer according to claim 2, characterized in that the Curie temperature difference of adjacent magnetocaloric materials is from 1.8 to 2.2 ° C. 4. Теплообменный слой по одному из пп.1-3, отличающийся тем, что в теплообменном слое присутствуют от 5 до 50 различных магнетокалорических материалов.4. The heat transfer layer according to one of claims 1 to 3, characterized in that from 5 to 50 different magnetocaloric materials are present in the heat transfer layer. 5. Теплообменный слой по одному из пп.1-3, отличающийся тем, что термические и/или электрические изоляторы состоят из органического полимера, керамики, неорганических оксидов, углеродных волокон или сетей углеродных волокон, различных сортов стекла, полупроводников или сочетания этих компонентов.5. The heat transfer layer according to one of claims 1 to 3, characterized in that the thermal and / or electrical insulators are composed of an organic polymer, ceramic, inorganic oxides, carbon fibers or networks of carbon fibers, various grades of glass, semiconductors or a combination of these components. 6. Теплообменный слой по одному из пп.1-3, отличающийся тем, что термические и/или электрические изоляторы образуют матрицу, в которую введены магнетокалорические материалы.6. The heat transfer layer according to one of claims 1 to 3, characterized in that the thermal and / or electrical insulators form a matrix into which magnetocaloric materials are introduced. 7. Теплообменный слой по одному из пп.1-3, отличающийся тем, что расстояние между соседствующими магнетокалорическими материалами составляет от 0,05 до 3 мм.7. The heat transfer layer according to one of claims 1 to 3, characterized in that the distance between adjacent magnetocaloric materials is from 0.05 to 3 mm. 8. Теплообменный слой по одному из пп.1-3, отличающийся тем, что магнетокалорические материалы и термические и/или электрические изоляторы образуют последовательность слоев, причем толщина слоев магнетокалорических материалов в каждом случае составляет от 1 до 100 мм.8. The heat exchange layer according to one of claims 1 to 3, characterized in that the magnetocaloric materials and thermal and / or electrical insulators form a sequence of layers, and the thickness of the layers of magnetocaloric materials in each case is from 1 to 100 mm. 9. Теплообменный слой по одному из пп.1-3, отличающийся тем, что он состоит из термомагнитных монолитов различных магнетокалорических материалов, в которых имеются сквозные каналы с площадью сечения отдельных каналов в пределах от 0,001 до 0,2 мм2 и толщиной стенки от 50 до 300 мкм, монолиты обладают пористостью в пределах от 10 до 60% и соотношением площади поверхности к объему в пределах от 3000 до 50000 м2/м3 или включают в себя одну или несколько параллельных пластин с толщиной от 0,1 до 2 мм и расстоянием между пластинами в 0,05-1 мм, или пакетированный теплообменный слой состоит из частиц термомагнитного материала, имеющих средний диаметр в пределах от 50 мкм до 1 мм и дающих в пакетированном слое пористость в пределах от 30 до 45%.9. The heat exchange layer according to one of claims 1 to 3, characterized in that it consists of thermomagnetic monoliths of various magnetocaloric materials, in which there are through channels with a cross-sectional area of individual channels ranging from 0.001 to 0.2 mm 2 and wall thickness from 50 to 300 microns, monoliths have porosity in the range from 10 to 60% and the ratio of surface area to volume in the range from 3000 to 50,000 m 2 / m 3 or include one or more parallel plates with a thickness of from 0.1 to 2 mm and the distance between the plates in 0.05-1 mm, or packaged heat the exchange layer consists of particles of thermomagnetic material having an average diameter ranging from 50 μm to 1 mm and giving a porosity in the packaged layer ranging from 30 to 45%. 10. Теплообменный слой по одному из пп.1-3, отличающийся тем, что пористость магнетокалорических материалов составляет 20-30%.10. The heat transfer layer according to one of claims 1 to 3, characterized in that the porosity of magnetocaloric materials is 20-30%. 11. Теплообменный слой по п.9, отличающийся тем, что площадь сечения отдельных каналов составляет от 0,01 до 0,03 мм2, а толщина стенки от 50 до 150 мкм.11. The heat transfer layer according to claim 9, characterized in that the cross-sectional area of the individual channels is from 0.01 to 0.03 mm 2 and the wall thickness is from 50 to 150 microns. 12. Теплообменный слой по одному из пп.1-3, отличающийся тем, что термомагнитные материалы выбирают из группы, которую образуют12. The heat transfer layer according to one of claims 1 to 3, characterized in that the thermomagnetic materials are selected from the group that form (1) Соединения с общей формулой (I)(1) Compounds with the general formula (I) ( A y B y − 1 ) 2 + δ C w D x E z   ( I )
Figure 00000001
 , ( A y B y - one ) 2 + δ C w D x E z ( I )
Figure 00000001
 , где параметры имеют следующие значения:where the parameters have the following meanings: А - Мn или Со,A is Mn or Co, В - Fe, Cr или Ni,B - Fe, Cr or Ni, С, D, Е по меньшей мере два из С, D, Е отличны друг от друга, концентрации их не исчезающе малы, иC, D, E at least two of C, D, E are different from each other, their concentrations are not vanishingly small, and они выбраны из группы, которую образуют Р, В, Se, Ge, Ga, Si, Sn, N, As и Sb, причем по меньшей мере один из С, D и Е представляет собой Ge или Si,they are selected from the group that P, B, Se, Ge, Ga, Si, Sn, N, As and Sb form, with at least one of C, D and E being Ge or Si, δ число в пределах от -0,1 до 0,1δ number ranging from -0.1 to 0.1 w, х, y, z числа в пределах от 0 до 1, причем w+х+z=1;w, x, y, z numbers ranging from 0 to 1, and w + x + z = 1; (2) соединения на основе La и Fe общих формул (II) и/или (III) и/или (IV)(2) compounds based on La and Fe of the general formulas (II) and / or (III) and / or (IV) L a ( F e x A l 1 − x ) 13 H y
Figure 00000002
 или L a ( F e x S i ) 1 − x 13 H y   ( I I )
Figure 00000003
 , L a ( F e x A l one - x ) 13 H y
Figure 00000002
 or L a ( F e x S i ) one - x 13 H y ( I I )
Figure 00000003
 , где х число от 0,7 до 0,95where x is a number from 0.7 to 0.95 y число от 0 до 3y is a number from 0 to 3 L a ( F e x A l y C o z ) 13   и л и   L a ( F e x S i y C o z ) 13   ( I I I )
Figure 00000004
 , L a ( F e x A l y C o z ) 13 and l and L a ( F e x S i y C o z ) 13 ( I I I )
Figure 00000004
 , где х число от 0,7 до 0,95where x is a number from 0.7 to 0.95 y число от 0,05 до 1-хy number from 0.05 to 1 z число от 0,005 до 0,5z is a number from 0.005 to 0.5 L a M n x F e 2 − x G e   ( I V )
Figure 00000005
 , L a M n x F e 2 - x G e ( I V )
Figure 00000005
 , где x число от 1,7 до 1,95, иwhere x is a number from 1.7 to 1.95, and (3) гейслеровские сплавы типа МnТР, где Т - это переходный металл, а Р металл с добавками р-типа и числом электронов на атом е/а в пределах от 7 до 8,5,(3) Geisler alloys of the MnTP type, where T is a transition metal, and P is a metal with p-type additives and the number of electrons per atom e / a in the range from 7 to 8.5, (4) соединения на основе Gd и Si общей формулы (V)(4) compounds based on Gd and Si of the general formula (V) G d 5 ( S i x G e 1 − x ) 4   ( V )
Figure 00000006
 , G d 5 ( S i x G e one - x ) four ( V )
Figure 00000006
 , где х число от 0,2 до 1where x is a number from 0.2 to 1 (5) соединения на основе Fe2P,(5) compounds based on Fe 2 P, (6) манганиты со структурой перовскита,(6) manganites with perovskite structure, (7) содержащие редкоземельные элементы соединения с общими формулами (VI) и (VII)(7) compounds containing rare earth elements with the general formulas (VI) and (VII) T b 5 ( S i 4 − x G e x )   ( V I )
Figure 00000007
 , T b 5 ( S i four - x G e x ) ( V I )
Figure 00000007
 , где х=0, 1, 2, 3, 4where x = 0, 1, 2, 3, 4 X T i G e   ( V I I )
Figure 00000008
 , X T i G e ( V I I )
Figure 00000008
 , где X=Dy, Но, Tm,where X = Dy, But, Tm, (8) соединения на основе Мn и Sb или As с общими формулами (VIII) и (IX)(8) compounds based on Mn and Sb or As with the general formulas (VIII) and (IX) M n 2 − x Z x S b   ( V I I I )
Figure 00000009
 M n 2 - x Z x S b ( V I I I )
Figure 00000009
 M n 2 Z x S b 1 − x   ( I X )
Figure 00000010
 , M n 2 Z x S b one - x ( I X )
Figure 00000010
 , где Z - Сr, Сu, Zn, Co, V, As, Ge,where Z is Cr, Cu, Zn, Co, V, As, Ge, х от 0,01 до 0,5,x from 0.01 to 0.5, причем Sb можно заменить на As, если только Z - это не As.moreover, Sb can be replaced by As, if only Z is not As. 13. Теплообменный слой по п.12, отличающийся тем, что магнетокалорический материал выбирают из по меньшей мере четвертичных соединений общей формулы (I), которые помимо Mn, Fe, P и при необходимости Sb дополнительно содержат Ge или As, или Si, или Ge и Si, или Ge и As, или Si и As, или Ge, Si и As.13. The heat transfer layer according to claim 12, characterized in that the magnetocaloric material is selected from at least quaternary compounds of the general formula (I), which, in addition to Mn, Fe, P and optionally Sb, additionally contain Ge or As, or Si, or Ge and Si, or Ge and As, or Si and As, or Ge, Si and As. 14. Способ изготовления теплообменных слоев по одному из пп.1-3, отличающийся тем, что порошок данного термомагнитного материала подвергают формовочной обработке для образования термомагнитного материала, а затем пакетируют материалы для формирования теплообменного слоя, предпочтительно перемежая их термическими и/или электрическими изоляторами, либо же интегрируют их в матрицу из термического и/или электрического изолятора.14. A method of manufacturing heat transfer layers according to one of claims 1 to 3, characterized in that the powder of a given thermomagnetic material is subjected to molding processing to form a thermomagnetic material, and then the materials are packaged to form a heat transfer layer, preferably alternating with thermal and / or electrical insulators, or integrate them into a matrix from a thermal and / or electrical insulator. 15. Применение теплообменного слоя по одному из пп.1-3 в холодильниках, кондиционерах, тепловых насосах или в производстве электроэнергии путем прямого преобразования тепла. 15. The use of the heat transfer layer according to one of claims 1 to 3 in refrigerators, air conditioners, heat pumps or in the production of electricity by direct heat conversion.
RU2012108925/07A 2009-08-10 2010-07-29 HEAT EXCHANGE LAYER FROM CASCADE OF MAGNETO-CALORIC MATERIALS RU2012108925A (en)

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EP09167550 2009-08-10
EP09167550.4 2009-08-10
PCT/EP2010/061025 WO2011018347A1 (en) 2009-08-10 2010-07-29 Heat exchanger bed made of a cascade of magnetocaloric materials

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